CN115193438A - Indium oxide composite material with nickel nanoparticles modified on surface and preparation method and application thereof - Google Patents

Indium oxide composite material with nickel nanoparticles modified on surface and preparation method and application thereof Download PDF

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CN115193438A
CN115193438A CN202210590674.6A CN202210590674A CN115193438A CN 115193438 A CN115193438 A CN 115193438A CN 202210590674 A CN202210590674 A CN 202210590674A CN 115193438 A CN115193438 A CN 115193438A
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indium oxide
nickel
composite material
preparation
hollow tubular
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CN115193438B (en
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曲家福
李松琦
胡俊蝶
杨晓刚
李长明
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Suzhou University of Science and Technology
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Suzhou University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
    • B01J35/23—
    • B01J35/39—
    • B01J35/61—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide

Abstract

The invention belongs to the technical field of nano composite materials, and particularly relates to an indium oxide composite material with a surface modified with nickel nanoparticles, and a preparation method and application thereof. Dissolving indium salt and 1,4-phthalic acid, uniformly stirring, heating for reaction, centrifugally drying, calcining at two sections, dispersing in a solvent, adding a nickel-containing precursor, mixing, heating for drying, and calcining the obtained product in different gas atmospheres to obtain the indium oxide composite material with the surface modified with the nickel nanoparticles. The composite material of the nickel nano particles modified on the surface of the indium oxide with the black hexagonal hollow tubular structure is a novel composite material with controllable structure, high light absorption efficiency, excellent performance and good stability, and has excellent performance on the photo-thermal catalytic carbon dioxide hydrogenation reaction; the raw materials used in the preparation method are low in cost, easy to obtain, simple and convenient in experimental operation, expensive equipment is not used in the whole process, and the industrial production is facilitated.

Description

Indium oxide composite material with nickel nanoparticles modified on surface and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to an indium oxide composite material with a surface modified with nickel nanoparticles, and a preparation method and application thereof.
Background
Energy is an important guarantee for promoting social development and scientific and technical progress, along with economic development and rapid industrialization, fossil fuels are consumed in large quantity, greenhouse effect is caused by serious standard exceeding of carbon dioxide content in the atmosphere, and solar-driven photo-thermal catalysis of carbon dioxide reduction to fuels or commodity chemicals is a promising strategy for meeting global energy requirements and relieving greenhouse effect. The carbon dioxide reduction comprises two parts of carbon dioxide activation and catalytic reduction, wherein an active site is required for adsorption and activation of carbon dioxide, and photo-generated electrons are required for catalytic reduction of carbon dioxide. Therefore, the design of high active sites and high surface area catalytic materials to promote carbon dioxide reduction has become a major concern.
Since the photo-thermal catalysis realized the photocatalytic decomposition of water in 1970, semiconductor photocatalysis has been widely studied by academia as a clean and pollution-free technology. The research field of semiconductor photocatalysis mainly relates to various fields such as energy, environment and the like, however, thermodynamic analysis shows that Gibbs free energy of partial complex chemical reactions is high and only can be excited by ultraviolet light, so that the utilization of solar spectrum is greatly limited.
The photo-thermal catalysis has three modes, wherein the first mode is a series connection mode of photocatalysis and thermocatalysis; the second is a photo-driven thermocatalytic reaction in which light merely serves to provide a source of heat, and in terms of the reaction mechanism, the nature of the reaction is a thermocatalytic process. The third is a thermally assisted photocatalytic reaction. Light plays a decisive role in the reaction process, and heating can promote the reaction rate to be improved.
The photocatalysis is mainly that the semiconductor photocatalyst is excited to generate electron holes under the action of illumination, then the electron holes respectively migrate to the surface of the catalyst to participate in the oxidation-reduction reaction, and the reaction path is different from that of the thermal catalysis. The main ways to determine photothermal catalysis are the following: 1. performance-temperature curves under photoreaction and dark reaction conditions. The surface temperature of the catalyst is tested by a thermocouple and the like, and whether the selectivity and yield of the products of photocatalysis and thermocatalysis are consistent under the same temperature condition is observed, if no difference exists, the part of the ultraviolet light in which the light can only play a heating role is not even utilized. If the difference is large, the light effect and the heat effect are obviously different. 2. Activation energy + photon utilization calculation. Whether the surface temperature measurement of the catalyst is accurate. In a macroscopic view, the local temperature of the nanoparticles cannot be reflected by measuring methods such as a thermocouple, and the performance may be improved due to the change of the local temperature.
When the photon energy is less than the silicon bandgap, light participates in the reaction primarily by providing a form of thermal energy; when the photon energy is larger than the silicon band gap, a part of photons excite the catalyst to generate electron-hole pairs to participate in the reaction, but most of the photons provide heat for the reaction again through a thermal relaxation mode.
Indium oxide is a highly efficient thermochemical catalyst with high selectivity to carbon monoxide, but its wide band gap characteristics (3.2 eV) make it unfavorable for light absorption and photothermal conversion, limiting its application to photothermal catalysis.
CN113398944B discloses a composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof, and the preparation method of the composite material of bismuth vanadate surface modified nickel cobaltate spinel comprises the steps of adding bismuth nitrate and ammonium metavanadate into an acidic solution, adjusting the pH value to 0.25-2, and heating for reaction to obtain decahedral bismuth vanadate; dispersing the decahedral bismuth vanadate in a solvent, adding a nickel cobaltate precursor, heating for reaction, centrifugally drying the obtained product, and calcining. The composite material of bismuth vanadate surface modified nickel cobaltite spinel is a novel composite material with controllable structure, high visible light absorption efficiency, excellent performance and good stability, and has excellent performance on photocatalytic water oxidation.
CN2021114345252 discloses a carbon cloth surface modified nickel cobaltate nanosheet array composite material of metal organic framework derivatization (MOF), and preparation and application thereof, specifically, the carbon cloth is soaked in a mixed solution of nitric acid and hydrochloric acid, then is put into a buffer solution, dopamine hydrochloride is added, and CC @ PDA is obtained after reaction; dipping the CC @ PDA into a soluble cobalt salt solution, adding a dimethyl imidazole solution, and reacting to obtain CC @ Co-MOF; adding soluble nickel salt solution, reacting and calcining; placing the calcined product into NaBH 4 And reacting in a solution to obtain the carbon cloth surface modified nickel cobaltate nanosheet array composite material. The composite material is a novel composite material with controllable structure, large specific surface area, excellent performance and good stability, and can be used for photocatalysis of CO 2 The reduction has excellent properties.
CN114225947A discloses a photocatalytic CO 2 The method comprises the following steps of reducing a graphite alkyne composite material for preparing fuel, wherein the graphite alkyne composite material is formed by compounding a precursor solution of NiIn2S4 and graphite alkyne, and the precursor solution of NiIn2S4 comprises a solvent, nickel salt, indium salt and a sulfur source; the NiIn2S 4/graphite alkyne composite material not only has the characteristics of excellent thermal stability, ultrahigh carrier mobility, high specific surface area, natural intrinsic band gap and the like of graphite alkyne, but also integrates the high catalytic activity of NiIn2S4, the heterojunction formed by the NiIn2S4 and the graphite alkyne widens the visible light absorption range, and the NiIn2S4 and the graphite alkyne are compounded to improve the photocatalytic CO 2 And (4) reduction.
CN113740390A discloses a nickel-doped indium oxide nanoparticle and a preparation method and application thereof. The nickel-doped indium oxide nanoparticles consist of indium oxide with nickel doped in the lattice of the indium oxide. Carrying out solvothermal reaction on an indium source, a nickel source and an organic ligand to obtain an In/Ni bimetallic MOF precursor, and annealing the In/Ni bimetallic MOF precursor to obtain nickel-doped indium oxide nanoparticles; wherein the molar quantity of the indium source is larger than that of the nickel source. Provided withPreparation of gas sensor pair NO by nickel-doped indium oxide nano-particles 2 The gas is sensitive.
Considering that the diffusion length of the host to the surface can be reduced by constructing the hollow structure, electron-hole separation is accelerated, multiple light scattering/reflection in the internal voids can increase light absorption, while increasing the surface area can promote carbon dioxide adsorption and surface catalysis. The nickel-loaded nano particles can provide more active sites, more oxygen vacancy active sites can be formed in the material by further utilizing hydrogen reduction, the material is changed into black, the light absorption range can be expanded, and the photo-thermal catalytic performance is improved.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of an indium oxide composite material with a surface modified with nickel nanoparticles, which comprises the following steps:
s11: adding indium salt and 1,4-phthalic acid into an organic solvent, and heating for reaction to obtain a hexagonal prism-shaped indium oxide metal organic framework material;
s12: calcining the hexagonal prism-shaped indium oxide metal organic framework material for two sections to obtain hexagonal hollow tubular indium oxide;
s13: placing the hexagonal hollow tubular indium oxide in a mixed gas atmosphere for reduction reaction to obtain black hexagonal hollow tubular indium oxide; the mixed gas consists of hydrogen and inert gas, and the volume ratio of the hydrogen to the inert gas is 4-6:96-94 parts of;
s14: and mixing the black hexagonal hollow tubular indium oxide and the nickel-containing precursor in water, drying and calcining to obtain the indium oxide composite material with the surface modified with the nickel nanoparticles.
Preferably, the indium salt is indium nitrate or indium chloride.
Preferably, the mass ratio of the indium salt to the 1,4-phthalic acid is 11-13: 11 to 13.
Further, the mass ratio of the indium salt to 1,4-phthalic acid is 1:1.
preferably, in the step S11, the solute is added in the mixed solution obtained by adding the indium salt and 1,4-phthalic acid to the organic solvent in an amount of 22 to 26mg/7 to 9ml of the organic solvent.
Further, indium salt and 1,4-phthalic acid were added to the mixed solution obtained after the addition of the indium salt to the organic solvent, and when the addition of the indium salt was 60mg and the addition of 1, 4-phthalic acid was 60mg, the addition of the organic solvent was 35 to 45ml in volume.
Specifically, indium salt and 1,4-phthalic acid were added to a mixed solution obtained after the addition of the indium salt to an organic solvent, and when the addition of the indium salt was 60mg and the addition of 1, 4-phthalic acid was 60mg, the volume addition of the organic solvent was 40ml.
Preferably, the organic solvent is N, N-dimethylformamide.
Preferably, in the step S11, the heating reaction temperature is 115 to 125 ℃ and the time is 20 to 60min.
Further, the temperature of the heating reaction is 120 ℃ and the time is 30min.
Further, in the step S11, a product obtained after the heating reaction is washed clean with ethanol, and then is placed in an oven for drying; the drying temperature is 60-90 ℃.
Specifically, the drying temperature is 80 ℃.
Preferably, in the step S12, the heating rate of the first stage of the two-stage calcination is 1-5 ℃/min, the temperature is 110-130 ℃, and the heat preservation time is 1-3 h; the temperature rise rate of the second stage of calcination is 1-5 ℃/min, the temperature is 450-550 ℃, and the heat preservation time is 1-3 h; the gas atmosphere of the two-stage calcination is air.
Further, in the step S12, the temperature rise rate of the first stage of the two-stage calcination is 2 ℃/min, the temperature is 120 ℃, and the heat preservation time is 2 hours; the temperature rise rate of the second stage of calcination is 2 ℃/min, the temperature is 500 ℃, and the heat preservation time is 2h.
Preferably, in step S13, the temperature of the reduction reaction is 200 to 400 ℃ and the time is 1 to 3 hours.
Further, in the step S13, the temperature of the reduction reaction is 300 ℃ and the time is 2 hours.
Preferably, in step S13, the concentration of the hydrogen gas is 5vt%.
Preferably, in step S14, the mass of nickel in the nickel-containing precursor is 2 to 20% of the mass of the black hexagonal hollow tubular indium oxide.
Further, the nickel-containing precursor is nickel acetylacetonate or nickel nitrate.
Preferably, in the step S14, the drying temperature is 60 to 90 ℃.
Further, in the step S14, the temperature of drying is 80 ℃.
Preferably, in step S14, the calcination conditions are: the gas atmosphere consists of hydrogen and inert gas, and the concentration of the hydrogen is 0-6 vt%; the heating rate is 1-5 ℃/min, the temperature is 200-400 ℃, and the time is 1-3 h.
Preferably, in step S14, the calcination conditions are: the gas atmosphere consists of an inert gas, excluding hydrogen; the heating rate is 2 ℃/min, the temperature is 300 ℃, and the time is 2h.
Preferably, in step S14, the calcination conditions are: the gas atmosphere consists of hydrogen and inert gas, and the concentration of the hydrogen is 5vt%; the heating rate is 2 ℃/min, the temperature is 300 ℃, and the time is 2h.
The invention also provides the indium oxide composite material with the surface modified with the nickel nano particles, which is prepared by the preparation method.
The invention also provides application of the indium oxide composite material with the surface modified nickel nano particles in photo-thermal catalytic carbon dioxide reduction.
Preferably, the application of the photo-thermal catalytic carbon dioxide reduction comprises the following steps:
s21: dispersing the indium oxide composite material with the surface modified with the nickel nanoparticles into an alcohol aqueous solution, coating the indium oxide composite material on conductive glass, and drying to obtain composite application conductive glass;
s22: placing the composite application conductive glass in a glass reactor, and introducing CO 2 And H 2 Then, a 300W xenon lamp is used for carrying out photo-thermal catalytic carbon dioxide reduction reaction;
s23: analysis of C by on-line gas chromatographO 2 Conversion, plotting the curves CO and CH 4 Standard curve to obtain CO and CH 4 The yield of (a).
Specifically, the application of the photo-thermal catalytic carbon dioxide reduction comprises the following steps:
dispersing 40-60 mg of material in 3-7 ml of mixed solvent of water and ethanol, uniformly dispersing by ultrasonic, then dropwise adding onto round (radius is 1.9 cm) conductive glass, drying at 50 ℃, transferring the obtained conductive glass into a customized glass reactor, sealing, degassing the reactor to remove air in the system, and injecting CO into the reactor after the reaction is finished 2 And H 2 (v: v = 1:4) until the pressure reached 90kPa, a performance test was performed using a 300W xenon lamp as simulated sunlight, light was condensed using a convex lens and temperature was monitored using an infrared temperature sensing device, and CO was analyzed by an online gas chromatograph equipped with a Flame Ionization Detector (FID) and a hot wire heat detector (TCD) 2 Conversion (every 1 h). After the test is finished, CO and CH are produced 4 Standard curve and obtaining CO and CH of the material according to the standard curve 4 Yield.
The method takes indium nitrate or indium chloride and 1,4-phthalic acid as solutes and N, N-dimethylformamide as a solvent, prepares the hexagonal prism-shaped indium oxide metal organic framework material by a simple oil bath method, converts the hexagonal prism-shaped indium oxide metal organic framework material into the hexagonal hollow tubular structure indium oxide by two-stage calcination, and finally obtains the black hexagonal hollow tubular structure indium oxide by high-temperature reduction in a hydrogen atmosphere. And then, the composite material of the black hexagonal hollow tubular structure indium oxide surface modified nickel nano particles is prepared by taking the composite material as a carrier material and nickel acetylacetonate or nickel nitrate as a precursor through high-temperature calcination under the protection of inert gas or high-temperature reduction under the atmosphere of hydrogen. The hollow structure inhibits the recombination of photo-generated electrons and holes, the modification of high-surface-area nickel nanoparticles and hydrogen reduction provide a large number of active sites, the black characteristic enlarges the light absorption range, and the photo-thermal catalysis performance is greatly improved.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the preparation method of the composite material with the nickel nano particles modified on the surface of the indium oxide with the black hexagonal hollow tubular structure, disclosed by the invention, has the advantages that the cost of raw materials is low, the raw materials are easy to obtain, the experimental operation is simple and convenient, expensive equipment is not used in the whole process, and the industrial production is facilitated;
2. the composite material of the nickel nano particles modified on the surface of the indium oxide with the black hexagonal hollow tubular structure, disclosed by the invention, is a novel composite material with a controllable structure, high light absorption efficiency, excellent performance and good stability, has excellent performance on the reduction of photo-thermal catalytic carbon dioxide, can be used for preparing fuels or commodity chemicals, and is very beneficial to industrial application.
3. Conventional In 2 O 3 The material is light yellow powder, and not only can increase CO by introducing oxygen defects 2 Can promote In at the same time 2 O 3 The light absorption capacity of the material, the color changes from light yellow to black.
Drawings
FIG. 1 shows h-In example 1 2 O 3 Transmission Electron Micrographs (TEMs);
FIG. 2 shows h-In example 1 2 O 3 Scanning Electron Micrographs (SEM);
FIG. 3 shows h-In example 2 2 O 3-Ov Transmission Electron Micrographs (TEMs);
FIG. 4 shows h-In example 2 2 O 3-Ov Scanning Electron Micrographs (SEM);
FIG. 5 shows Ni/h-In example 3 2 O 3-Ov Transmission Electron Micrographs (TEMs);
FIG. 6 shows Ni/h-In example 3 2 O 3-Ov Scanning Electron Micrographs (SEM);
FIG. 7 photo-thermocatalytic CO of the material prepared in example 9 2 The effect diagram of hydrogenation.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
Hexagonal hollow tubular structure indium oxide (h-In) 2 O 3 ) The preparation method comprises the following specific steps:
adding 60mg of indium nitrate and 60mg of 1,4-phthalic acid into 40ml of N, N-dimethylformamide, stirring vigorously at room temperature, transferring to an oil bath kettle, reacting at 120 ℃ for 30min, washing a reaction product with ethanol, drying In a drying oven, further calcining the dried product In a tube furnace at 120 ℃ for 2h at a temperature rise rate of 2 ℃/min to 500 ℃ for 2h at a temperature rise rate of 2 ℃/min, and thus obtaining In 2 O 3 . In thus obtained 2 O 3 The TEM image is shown In FIG. 1, the SEM image is shown In FIG. 2, in can be seen from the SEM image 2 O 3 Was successfully prepared and was uniform in size.
Example 2
Black hexagonal hollow tubular indium oxide (In) 2 O 3-Ov ) The preparation method comprises the following specific steps:
conventional In 2 O 3 The material is light yellow powder, and not only can increase CO by introducing oxygen defects 2 Can promote In at the same time 2 O 3 The light absorption capacity of the material changes from light yellow to black. Firstly, the In prepared above is taken 2 O 3 100-300mg of the material is put into a crucible, the crucible is placed in a 5% hydrogen atmosphere for calcination, the morphology of the material is accurately controlled by regulating and controlling the reduction temperature, so that the material keeps the original hexagonal hollow tubular structure, and experiments show that the optimal temperature is 300 ℃ and the heating rate is 2 ℃/min. The resulting material, such as the TEM and SEM of fig. 3 and 4, can be seen to have unchanged morphology after the introduction of oxygen defects.
Example 3
Composite material (Ni/h-In) of nickel nano particles modified on surface of indium oxide with black hexagonal hollow tubular structure 2 O 3-Ov ) The preparation method of the composite material comprises the following specific steps:
100mg of h-In prepared as described In example 2 above were taken 2 O 3-Ov And 2Dispersing 4.65mg of nickel acetylacetonate hexahydrate into 10ml of water, stirring for 20-40 min under a vacuum condition, drying In water bath at 60-90 ℃ after the completion, putting the dried sample into a tubular furnace, calcining for 1-3 h at 200-400 ℃ under the protection of inert gas, wherein the heating rate is 1-5 ℃/min, and finally obtaining Ni/h-In 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading quantities 2 O 3-Ov The composite material is the indium oxide composite material of the surface modified nickel nano particles.
The obtained Ni/h-In 2 O 3-Ov The TEM image and the SEM image of the composite material are shown in FIG. 5 and FIG. 6, and it can be seen that the nickel nanoparticles are granular and successfully modified on the hexagonal hollow structure indium oxide.
Example 4
Composite material (Ni/h-In) of nickel nano particles modified on surface of indium oxide with black hexagonal hollow tubular structure 2 O 3-Ov ) The preparation method of the composite material comprises the following specific steps:
100mg of h-In prepared as described In example 2 above were taken 2 O 3-Ov And 21.78mg of nickel acetylacetonate into 10ml of water, stirring for 20-40 min under a vacuum condition, drying In water bath at 60-90 ℃ after the completion, putting the dried sample into a tubular furnace, calcining for 1-3 h at 200-400 ℃ under the protection of inert gas, wherein the heating rate is 1-5 ℃/min, and finally obtaining Ni/h-In 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading quantities 2 O 3-Ov A composite material. The obtained Ni/h-In 2 O 3-Ov The TEM image and the SEM image of the composite material are shown in FIG. 5 and FIG. 6, and it can be seen that the nickel nanoparticles are granular and successfully modified on the hexagonal hollow indium oxide.
Example 5
Composite material (Ni/h-In) of nickel nano particles modified on surface of indium oxide with black hexagonal hollow tubular structure 2 O 3-Ov ) The preparation method of the composite material comprises the following specific steps:
take 100mg aboveh-In prepared In the following example 2 2 O 3-Ov And 24.65mg of nickel acetylacetonate hexahydrate are dispersed In 10ml of water, then stirred for 20min under the vacuum condition, after the drying is finished, the water bath drying is carried out at 60 ℃, the dried sample is put into a tubular furnace, the calcination is carried out at 200 ℃ for 1h under the protection of inert gas, the heating rate is 1 ℃/min, and finally the Ni/h-In is obtained 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading quantities 2 O 3-Ov The composite material is the indium oxide composite material of the surface modified nickel nano particles.
Example 6
Composite material (Ni/h-In) of nickel nano particles modified on surface of indium oxide with black hexagonal hollow tubular structure 2 O 3-Ov ) The preparation method of the composite material comprises the following specific steps:
100mg of h-In prepared as described In example 2 above were taken 2 O 3-Ov And 21.78mg of nickel acetylacetonate into 10ml of water, stirring for 40min under a vacuum condition, drying In a water bath at 90 ℃, putting the dried sample into a tubular furnace, calcining for 3h at 400 ℃ under the protection of inert gas at the temperature rise rate of 5 ℃/min to finally obtain Ni/h-In 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading quantities 2 O 3-Ov A composite material.
Example 7
Composite material (Ni/h-In) of nickel nano particles modified on surface of indium oxide with black hexagonal hollow tubular structure 2 O 3-Ov ) The preparation method of the composite material comprises the following specific steps:
100mg of h-In prepared as described In example 2 above were taken 2 O 3-Ov And 24.65mg of nickel acetylacetonate hexahydrate are dispersed In 10ml of water, then stirred for 40min under the vacuum condition, after the drying is finished, the water bath drying is carried out at 90 ℃, the dried sample is put into a tubular furnace, the calcination is carried out at 400 ℃ for 3h under the protection of inert gas, the heating rate is 5 ℃/min, and finally the Ni/h-In is obtained 2 O 3-Ov Composite material and by adjusting Ni 2+ The amount of the precursor is differentSupported amount of Ni/h-In 2 O 3-Ov The composite material is the indium oxide composite material of the surface modified nickel nano particles.
Example 8
Composite material (Ni/h-In) of nickel nano particles modified by indium oxide with black hexagonal hollow tubular structure surface 2 O 3-Ov ) The preparation method of the composite material comprises the following specific steps:
100mg of h-In prepared as described In example 2 above were taken 2 O 3-Ov And 21.78mg of nickel acetylacetonate into 10ml of water, stirring for 20min under a vacuum condition, drying In a water bath at 60 ℃ after the completion, putting the dried sample into a tube furnace, calcining for 1h at 200 ℃ under the protection of inert gas, wherein the heating rate is 1 ℃/min, and finally obtaining Ni/h-In 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading quantities 2 O 3-Ov A composite material.
Example 9
Photo-thermal catalysis of CO under visible light conditions 2 And (3) testing the performance, which comprises the following specific steps:
on-line evaluation of the materials obtained in examples 1 to 3 for photo-thermocatalytic CO by means of the LabSolar-6A (Pofely, beijing) System 2 And (5) testing the hydrogenation performance. Dispersing 50mg of the material in 5ml of a mixed solvent of water and ethanol, uniformly dispersing the material by ultrasonic waves, dropwise adding the material onto round (the radius is 1.9 cm) conductive glass, drying the glass at 50 ℃, transferring the obtained conductive glass into a customized glass reactor, sealing the glass reactor, degassing the reactor to remove air in the system, and injecting CO into the reactor after the reaction is finished 2 And H 2 (v: v = 1:4) until the pressure reached 90kPa, a performance test was performed using a 300W xenon lamp as simulated sunlight, light was condensed using a convex lens and temperature was monitored using an infrared temperature sensing device, and CO was analyzed by an online gas chromatograph (GC D7900P) with FID and TCD detectors 2 Conversion (every 1 h). After the test, CO and CH are produced 4 Standard curve and obtaining CO and CH of the material according to the standard curve 4 Yield. FIG. 7 shows the materials obtained in examples 1 to 3Photo-thermal catalysis of CO 2 The effect diagram of hydrogenation. As can be seen from FIG. 7, ni/h-In 2 O 3-Ov The composite material has excellent photo-thermal catalysis CO 2 Hydrogenation activity, wherein the yield of the optimal catalyst CO is 180mmol · g · h -1 The composite material has the advantages of excellent performance, good stability, simple preparation process, low raw material price and easy industrial production.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. A preparation method of an indium oxide composite material with a surface modified with nickel nanoparticles is characterized by comprising the following steps:
s11: adding indium salt and 1,4-phthalic acid into an organic solvent, and heating for reaction to obtain a hexagonal prism-shaped indium oxide metal organic framework material;
s12: calcining the hexagonal prism-shaped indium oxide metal organic framework material for two sections to obtain hexagonal hollow tubular indium oxide;
s13: placing the hexagonal hollow tubular indium oxide in a mixed gas atmosphere for reduction reaction to obtain black hexagonal hollow tubular indium oxide; the mixed gas consists of hydrogen and inert gas, and the volume ratio of the hydrogen to the inert gas is 4-6:96-94 parts of;
s14: and mixing the black hexagonal hollow tubular indium oxide and the nickel-containing precursor in water, drying and calcining to obtain the indium oxide composite material with the surface modified with the nickel nanoparticles.
2. The method of claim 1 wherein the mass ratio of indium salt to 1,4-benzenedicarboxylic acid is from 11 to 13:11 to 13.
3. The method according to claim 1, wherein the heating reaction is carried out at 115-125 ℃ for 20-60 min in step S11.
4. The preparation method according to claim 1, wherein in step S12, the first stage calcination temperature of the two-stage calcination is 110 to 130 ℃ and the time is 1 to 3 hours; the second stage calcining temperature is 450-550 ℃ and the time is 1-3 h.
5. The method according to claim 1, wherein the reduction reaction is carried out at a temperature of 200 to 400 ℃ for 1 to 3 hours in step S13.
6. The method according to claim 1, wherein in step S14, the mass of nickel in the nickel-containing precursor is 2 to 20% of the mass of the black hexagonal hollow tubular indium oxide.
7. The method of claim 1 or 6, wherein the nickel-containing precursor is nickel acetylacetonate or nickel nitrate.
8. The method of claim 1, wherein in step S14, the calcining conditions are: the gas atmosphere consists of hydrogen and inert gas, and the concentration of the hydrogen is 0-6 vt%; the temperature is 200-400 ℃ and the time is 1-3 h.
9. An indium oxide composite material of surface-modified nickel nanoparticles prepared by the preparation method of any one of claims 1 to 8.
10. Use of the indium oxide composite with surface-modified nickel nanoparticles of claim 9 for photo-thermal catalytic carbon dioxide reduction.
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